CA1223732A

CA1223732A - Method of preparing an aqueous slurry of solid carbonaceous fuel particles and an aqueous slurry so prepared

Info

Publication number: CA1223732A
Application number: CA000461489A
Authority: CA
Inventors: Mait M. Mathiesen; Kent O. Svensson
Original assignee: Berol Kemi AB; Carbogel AB
Current assignee: Carbogel AB; Nouryon Surface Chemistry AB
Priority date: 1983-08-26
Filing date: 1984-08-21
Publication date: 1987-07-07
Also published as: DK177285A; GB8323011D0; AU3218984A; US4627855A; IT1176617B; EP0154636A1; ZA846103B; IT8422362A0; DK177285D0; JPS60502212A; WO1985001059A1; BR8407038A

Abstract

Abstract of the Disclosure:

The surfaces of solid fuel particles, in a solid fuel particle slurry in water, are oxidised by exposure to the action of an oxidising agent, representatively potassium permanganate, to alter the characteristics thereof and permit the employment of reduced amounts of surface-active agent for purposes of attaining de-sired characteristics of the slurry, which slurry also comprises a part of the invention as disclosed.

Description

~2~ 7~

The predominan~ly hydrophobic nature of surfaces of particulate solid fuel such as coal, solid refinery byproducts, and coke is often utilized in order to at-tach dispersant molecules to said surfaces which, when added in sufficlent amounts, render the composition of solid fu~l particles, water and dispersant pumpable.
A composition including approximately 20 to 35~ w/w of water and 80 to 65% solid fuel particles with a maxi~
mum si.ze ranging from 10 to 300 microns requires ap-proxima-tely 0.15 to 0.85~ w/w of water-soluble surface active dispersant to attain sufficient flow. The disper-sant concentration is in each case dependent on the available surface area of solid fuel particles, which varies with the surface structure and the particle size distribution.
It has now surprisingly been found that a condition-ing of solid fuel particles in water with water-soluble oxidising agents such asl for example, potassium perman-~anate or hydrogen peroxide, brings about a change in the surface properties of the solid fuel so that the amounts of dispersant required for preparin~ a slurry of the solid fuel particles and water are significantly reduced The selection of oxidant and suitable amounts thereof are readily established by one skilled in the art.
In other connections, it is previously known to oxidize coal and similar materials for other purposes.

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As examples of the prior art technique mention may be made of the following patent specifications:
US-4,261,701 relates to an inexpensive dispersant for coal suspensions which consists of the reaction product of (1) polycyclic polycarboxylic acic1s, and ~2) a base, such as sodium hydroxide rrhe polycyclic carboxylic acids are obtained by oxidation of coal.
The coal which constitutes the solid fuel phase in the coal suspension is not oxidized according to the pa-tent specification.
US-4,305,728 and 4,403,998 correspond to US 4,261,701, with the difference however that the dispersant is the coal proper in the coal suspension, i.e. the coal in the suspension is oxidized with oxygen or nitric acid for formation of polycyclic carboxylic acids and is then rea;cted with a base, such as sodium hydroxide.
VS-3,632,479 relates to the surface oxidation of coal at elevated temperature to prevent agglomeration.
US-4,203~728 relates to the surface oxidation of coal in an oil-coal suspension.
DE~3,246,499 relates to the electrochemical conver-sion of coal by alternating anodic oxidation and catho-dic reduction.
US-4,332,593 and 4,406,664 relate to the hydro-phobization of coal particles by means of a peroxide catalyzed polymerization process~
GB-17,729 of 1913 relates to the production of a colloidal solution or emulsion of coal by grinding.

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It is stated that the coal is decomposed into coal mo-lecules and that this is realized by electrical friction forces or by means of tannin, formalin, potassium per-manganate, chromic acid or the like.
The invention differs from the prior art in that the carbonaceous material is first subjected to a treat-ment with an oxidant, and that a dispersant is added to the thus conditioned material in conjunction with or directly after the oxidation treatment, the requisite amount of dispersant being drastically reduced by the oxidation treatment I-t has been found that for a slurry which contains about 65-80~ by weight of carbonaceous material and the rest water and additives such as dis-persants, stabilizers, pH adjusting agents and the like, the amount of dispersants may very often be reduced to less than half the amount required to bring about the same stability and ~lowability properties of a corre-sponding slurry, but with carbonaceous material that has not been oxidation-treated. This implies that the amount of dispersant in the present invention generally can be reduced to be at most about 0.5% by weight based on the slurry weight, preferably at most about 0.3~ by weight.
By the present invention there is provided a method of preparing an aqueous slurry of solid carbonaceous fuel particles by suspending the particles in water with the aid of a dispersion~producing amount of a water-soluble surface~active dispersant, wherein -the surfaces of said solid carbonaceous fuel particles are concli-. , ~ 4 -23'732 tioned by exposing them to the action of an oxidising agent, and the water-soluble surface~active dispersant is added to the thus conditioned fuel particles.
In the preferred embodiments of the method according-ing to the invention the surfaces of said fuel particl~s are exposed to a chemical oxidising agent other than air; the oxidising agent is water-soluble; the oxidising agent is selected from the group consisting of potassium permanganate 9 hydrogen peroxide, oxygen, ozone, chromic acid, hyphochlorous acid, or an organic oxidising agent;
the oxidising agent is potassium permanganate; the amount of oxidising agent employed is about one mole per mole of surface~active dispersant employed; the amount of oxidising agent is from about 0.0001 to 0.1% by weight based upon the weight of the solid fuel particles in the slurry; the amount of oxidising agent is from about 0.001% to about 0.03% by weight based upon the weight of the solid fuel particles in the slurry; the solid carbonaceous fuel particles are exposed to the oxidising agent in the form of a dilute suspension which is there-after dewatered; the surface-active dispersant is admixed with the solid carbonaceous fuel particles subsequent -to the oxidising step; the solid carbonaceous fuel par ticle surfaces are exposed to the action of the oxidis-ing agent concurrently with the dispersant in a mixing step; finer solid carbonaceous fuel particles are treat-ed separately with a different amount of oxidising agent than coarser solid carbonaceous fuel particles; and ~;~23~ 2 the finer particles have a maximum diameter of about 30 microns and the coarser particles have a maximum diameter of about 300 microns.
According to the invention there is also provided an aqeuous slurry of solid carbonaceous fuel particles, a dispersion-producing amount of a water-soluble surface-active dispersant and water, wherein the solid carbo-naceous fuel particles have partially oxidised surfaces.
In the preferred embodiments of the aqueous slurry according to the invention the partially oxidised sur-faces of the fuel particles have been oxidised by ex-posure to a chemical oxidising agent other than air;
the partially oxidised surfaces of the fuel particles have been oxidised by exposure to potassium permanganate;
the slurry is a mixture of finer solid fuel particles and coarser solid fuel particles, each of which groups of particles has been separately treated with oxidising agent for oxidation of the surfaces thereof and there-after combined; the f~ner particles have a maximum dia-meter of about 30 microns and the coarser particles have a maximum diameter of about 300 microns; the slurry comprises about 65-80% by weight of solid carbonaceous fuel particles, the rest being water and additives in-cluding not more than about 0.5% by weight of water soluble surface-active dispersant; and the amount of dispersant is not more than about 0,3% by weight.
Further details and features of the invention will appear from the following specifica~ion and the appended claims.

In general, the invention is preferably carried out in either of the following ways:
1. The solid fuel particles are suspended in water by means of mechanical agitation, prior to dewatering to the final desired moisture content. At this stage of the slurry manufacturing process, the selected amount of oxidant - in the case of KMnO~ about 0.001~ to 0.03~
by weight on solid fuel weight ~ is added to the dilute suspension. Retention time is less critical inasmuch as the surface oxidation proceeds rapidly to the desired level as determined by the selection of the amount of oxidant employed.
After conditioning, the dilute suspension is dewa-tered by conventional means to a moisture content of about 15 to 35~ by weight. The dewatered product is then admixed with the selected dispersant; the amounts of dispersant now being reduced by the partial oxida-tion, and a pumpable slurry product is produced.
~ fter production of the pumpable slurry, a further quantity of oxidant - about 50% or less of the original quantity employed - may be added to the slurry to ensure that an excess of oxidant is present to maintain a pro-per balance between oxidised portions of the particle surfaces and the reduced amount of dispersant used.

2. Particularly if the solid fuel particles dis-play limited porosity~ and therefore limited effective surface area~ the oxidant may be added simultaneously with the dispersing agent in the final mixing process.

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The rate of oxida-tion is far higher than the rate of dispersant absorption, as shown in experiments.

3. In cases where the solid fuel particles are porous, and therefore consume extreme quantities of dispersing agent if not pretreated with oxidant, it is preferred to employ a different procedure:
The oxidant used in the conditioning stage prior to dewatering is employed in larger quantity (over 0.01-6 by weight of solid fuel weight) in order to ensure ef-fective oxidation of the entire particle surface in-cluding pore surfaces.
The solid fuel is thus well oxidised and displays little affinity to surface active dispersing agents in that state or at that stage. When mixing the slurry after dewatering, the moist particles (at about 15 - 35%
~oisture content) are mechanically agitated prior to dispersant addition, whereby the outer surfaces of the particles by means of shear and attrition become increas-ingly hydrophobic, and thus effective anchoring sites for dispersants. The mechanical agitation is carried out to the extent that is required as determined by testing the amount of dispersant required to achieve a pumpable slurry, a procedure easily executed by one skilled in the art.
~ . In cases where the solid fuel particles display a size distribution with relatively high amounts of very fine particles, which represent the majority of the available particle surface area, it is preferred to treat the finer fractions separately with a different, .,, 3~3Z

preferably higher, amount of oxidant than the coarser particles. Normally, it is preferred to treat the par-ticles of a maximum size of about 5 to 30 micron dia-meter differently than those reaching a maximum of about 50 to 300 micron diameter. It is also important to note the following:
In order to reduce the impurities content (i.e., mineral matter including inorganic sulphur~containing species), the solid fuel may have to be divided into extremely fine size, down to about minus 20 micron size (i.e., maximum size of 20 microns) or less. This makes possible the liberation of very fine inorganic species in the fuel. A slurry of this size distribution, how-ever, requires high dispersant levels owing to the very large surface area of the particles, and preoxidation will reduce this dispersant requirement considerably, while producing a slurry of sufficiently favourable rheological properties without incurring prohibitive dispersant cost.

A 200 g sample of coal particles (Terry Eagle coal ex Hanna Mining Company, Virginia) of 160 micron top size was slurried with water and an ethoxylated dinonyl-phenol disperant ~degree of ethoxylation = 70) and required 0.55% by weight of dispersant on slurry weight to reach sufficient fluidity at 73% coal content; i.e., a viscosity of less than 1000 CPS at 30 s shear rate.

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An iden~ical coal sample was then conditioned with 0.008~ of KMnO4 (w/coal w) dissolved in the slurry water while adding dispersant to the mixture. This slurry reached sufficient fluidity at 0~22~ of dispersant on slurry weight.

E~AME'LES 2- ~
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The following oxidising agents are employed in the procedure of Example 1 with e~ual facility and with equal success: Hydrogen peroxide, oxygen, ozone, and hypochlorous acid, as well as the organic peroxldes benzoyl peroxide and tertiary-butyl hypochlorite Others may also be used if desired, e.g., chromic acid.
Based upon the weight of the solid fuel particles involved in the slurry, the operative ranges for the various oxidising agents employed accoxding to the pre sent invention are as follows:
Potassium permanganate 0~001% to about 0.03 Hydrogen peroxide0.0003% to about 0.01 Oxygen 0.0001~ to about 0.005 Ozone 0.0005% to about 0.02%
Hypochlorous acid0.0005~ to about 0.02%
Benzoyl peroxide0.0006~ to about 0.04%
Tertiary-butyl hypochlorite 0.0006% to about 0.04~
When oxygen is used as the oxidising agent according to the invention, it is according to usual procedure dissolved and reacted in the presence of a catalyst, such as copper or manganese vanadate. The general range of oxidant, which in all cases should be water-sol-lble, 3~

is on the order of 0.0001% to about 0.1%, based on the solid fuel particle weight, and an excess over such amounts is generally recommended in order co~pletely to oxidise pore surfaces or at least more completely oxidise the same.
The invention is valuable in that it siqnificantly reduces the cost of preparing a slurry, in addition to which the viscosity of the slurry is reduced as com-pared to a slurry which reaches Eluidity at a higher dispersant concentration, i.e., a slurry in which the coal or solid fuel particles have not been treated with oxidant.
Although the applicants do not wish to be limited by any theory of operation, it is believed that exposure of the surfaces of the individual solid fuel particles to the oxidising agent reduces the number of hydrophobic sites for attachment thereto of the hydrophobic end of the dispersing surface-active agent, thereby reducing the number of sites to which the hydrophobic end of the dispersing surface-active agent can attach itself on an individual particle surface and, moreover, it is believed that the oxidation of the surface of the individual solid fuel particles also introduces, to a certain extent at least, additional hydrophilic sites directly on the solid fuel par-ticles surface itself.
This would at least offer a partial explanation for the fact that pumpable, flowable, and stable slurries are attained, with the employment of this oxidation ~223~3~

step, which require lesser amounts of dispersing surface-active agent for purposes of attaining the same desir-able characteristics of dispersability, pumpability, and stability in the ultimate slurry, than the same composition without the oxidation feature.
The amount of the oxidant to be used is generally determined by the properties of the coal surface. It is generally useful to balance the amount of oxidant and the amount of dispersant in such a way that one mole of oxidant, e.g. K~lnO4, is considered equivalent to one mole of dispersant used. ~hus, the amount of dispersant rendered superfluous can be eliminated and/or any excess controlled.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE:
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method of preparing an aqueous slurry of about 65 to about 80% by weight of solid carbonaceous fuel particles consisting essentially of the following steps:
(a) conditioning the surfaces of said solid car-bonaceous fuel particles by exposing them to the action of a reagent consisting essentially of at least about 0.0001% by weight, based upon the weight of the solid fuel particles, of a water-soluble chemical oxidising agent other than air to oxidise said surfaces and make them more hydrophilic and (b) suspending the thus-conditioned carbonaceous fuel particles in water with the aid of a dispersion-producing amount of a water-soluble surface-active dispersant, provided, however, that when the oxidising agent is oxygen, it is used in the presence of a catalyst.

2. A method as claimed in claim 1, wherein the oxidising agent is selected from the group consisting of potassium permanganate, hydrogen peroxide, oxygen plus a catalyst, ozone, chromic acid, hypochlorous acid, or an organic oxidising agent.

3. A method as claimed in claim 1, wherein the oxidising agent is potassium permanganate.

4. A method as claimed in claim 1, wherein the amount of oxidising agent employed is about one mole per mole of surface-active dispersant employed.

5. A method as claimed in claim 1, wherein the amount of oxidising agent is from about 0.0001 to 0.1% by weight based upon the weight of the solid fuel particles in the slurry.

6. A method as claimed in claim 5, wherein the amount of oxidising agent is from about 0.001% to about 0.03% by weight based upon the weight of the solid fuel particles in the slurry.

7. A method as claimed in claim 1, wherein the solid carbonaceous fuel particles are exposed to the oxidising agent in the form of a dilute suspension which is thereafter dewatered.

8. A method as claimed in claim 1, wherein the surface-active dispersant is admixed with the solid carbonaceous fuel particles subsequent to the oxidising step.

9. A method as claimed in claim 1, wherein the solid carbonaceous fuel particle surfaces are exposed to the action of the oxidising agent concurrently with the disper-sant in a mixing step.

10. A method as claimed in claim 1, wherein finer solid carbonaceous fuel particles are treated separately with a different amount of oxidising agent than coarser solid carbonaceous fuel particles.

11. A method as claimed in claim 10, wherein the finer particles have a maximum diameter of about 30 microns and the coarser particles have a maximum diameter of about 300 microns.

12. An aqueous slurry consisting essentially of (a) about to about 80% by weight of solid carbonaceous fuel particles, which have been conditioned to partially oxidise the surfaces thereof and make them more hydrophilic by exposing said particles to at least about 0.0001% by weight, based upon the weight of the solid fuel particles, of a water-soluble chemical oxidising agent other than air, (b) a dispersion-producing amount of a water-soluble surface-active dispersant, and (c) water, provided, however, that when the oxidising agent is oxygen, it is used in the presence of a catalyst.

13. An aqueous slurry as claimed in claim 12, wherein the partially oxidised surfaces of the fuel particles have been oxidised by exposure to potassium permanganate.

14. An aqueous slurry as claimed in claim 12, wherein the slurry is a mixture of finer solid fuel particles and coarser solid fuel particles, each of which groups of particles has been separately treated with oxidising agent for oxidation of the surfaces thereof and thereafter combined.

15. An aqueous slurry as claimed in claim 14, wherein the finer particles have a maximum diameter of about 30 microns and the coarser particles have a maximum diameter of about 300 microns.

16. An aqueous slurry as claimed in claim 12, wherein the slurry includes not more than about 0.5% by weight of water-soluble surface-active dispersant.

17. An aqueous slurry as claimed in claim 16, wherein the amount of dispersant is not more than about 0.3% by weight.